CN1294169C - Process for improving water-whitening resistance of pressure sensitive adhesives - Google Patents
Process for improving water-whitening resistance of pressure sensitive adhesives Download PDFInfo
- Publication number
- CN1294169C CN1294169C CNB028178394A CN02817839A CN1294169C CN 1294169 C CN1294169 C CN 1294169C CN B028178394 A CNB028178394 A CN B028178394A CN 02817839 A CN02817839 A CN 02817839A CN 1294169 C CN1294169 C CN 1294169C
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- China
- Prior art keywords
- alkyl
- monomer
- water
- polymerizable surfactants
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims abstract description 112
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 136
- 239000000178 monomer Substances 0.000 claims abstract description 134
- 239000000839 emulsion Substances 0.000 claims abstract description 118
- 239000004094 surface-active agent Substances 0.000 claims abstract description 118
- -1 alkyl methacrylate ester Chemical class 0.000 claims abstract description 64
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical group NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 123
- 239000004816 latex Substances 0.000 claims description 74
- 229920000126 latex Polymers 0.000 claims description 74
- 238000006116 polymerization reaction Methods 0.000 claims description 71
- 125000004432 carbon atom Chemical group C* 0.000 claims description 61
- 125000000217 alkyl group Chemical group 0.000 claims description 58
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 28
- 125000003342 alkenyl group Chemical group 0.000 claims description 28
- 239000007858 starting material Substances 0.000 claims description 26
- 150000005215 alkyl ethers Chemical class 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 229920001567 vinyl ester resin Polymers 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 16
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 16
- 229910052728 basic metal Inorganic materials 0.000 claims description 13
- 150000003818 basic metals Chemical class 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 230000009466 transformation Effects 0.000 claims description 11
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 239000004821 Contact adhesive Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229920000847 nonoxynol Polymers 0.000 claims description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 5
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 claims description 4
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 claims description 4
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 4
- BVDBXCXQMHBGQM-UHFFFAOYSA-N 4-methylpentan-2-yl prop-2-enoate Chemical compound CC(C)CC(C)OC(=O)C=C BVDBXCXQMHBGQM-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 4
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims 4
- 239000002245 particle Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000004908 Emulsion polymer Substances 0.000 abstract 1
- 239000002954 polymerization reaction product Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 18
- 229920006267 polyester film Polymers 0.000 description 17
- 239000002585 base Substances 0.000 description 10
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007844 bleaching agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002356 laser light scattering Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical group CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UOMQUZPKALKDCA-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UOMQUZPKALKDCA-UHFFFAOYSA-K 0.000 description 1
- NCTBYWFEJFTVEL-UHFFFAOYSA-N 2-methylbutyl prop-2-enoate Chemical compound CCC(C)COC(=O)C=C NCTBYWFEJFTVEL-UHFFFAOYSA-N 0.000 description 1
- WHGXZPQWZJUGEP-UHFFFAOYSA-N 2-prop-1-enylphenol Chemical compound CC=CC1=CC=CC=C1O WHGXZPQWZJUGEP-UHFFFAOYSA-N 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 1
- 235000021322 Vaccenic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical group CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- HLMAOUJZLUOWAH-UHFFFAOYSA-N ethenyl acetate 2-methylpropanoic acid Chemical compound C(=C)OC(C)=O.C(C(C)C)(=O)O HLMAOUJZLUOWAH-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Pressure sensitive adhesive compositions having enhanced resistance to water-whitening comprising an aqueous emulsion polymer are disclosed. The polymer comprises the polymerization reaction product of a polymerizable aqueous emulsion comprising: (i) at least one hydrophobic alkyl acrylate or alkyl methacrylate ester of an alcohol, (ii) at least about 1 Wt. % of at least one hydrophilic monomer, (iii) at least about 5 wt. % of at least one partially hydrophilic alkyl acrylate or alkyl methacrylate ester of an alcohol, and (iv) a water-soluble or water-dispersible polymerizable surfactant selected from compounds having a terminal allyl amine moiety, substituted phenyl compounds having at least one alkenyl substituent, polyoxyalkylene-1- (allyloxymethyl) alkyl ether sulfate salts, or mixtures thereof, and the average particle size of the polymer is less than or equal to 200 nm. Also disclosed are processes for preparing same.
Description
The cross reference of related application
This application is a non-provisional application, and it requires the right of priority of provisional application 60/305,174 (submission on July 13 calendar year 2001) and 60/323,984 (submission on September 21 calendar year 2001) formerly, and it openly is hereby incorporated by.
Background technology
The present invention relates to method based on pressure sensitive adhesive and this tackiness agent of preparation of aqueous emulsion.Pressure sensitive adhesive of the present invention have raising water-fast-(water-whitening) property bleaches.
These pressure sensitive adhesives are specially adapted to require pressure sensitive adhesive to keep fusible application between base material and plane materiel when standing hot water spray or dipping.The hot water binding property is requirement in the application of for example bottle label etc., and wherein bottle will stand hot water spray in washing operation.Generally speaking, when pressure sensitive adhesive contact water with transparent plane materiel or base material or high humidity, water-whitening resistance is desirable.Example comprises the label on truck side, signboard and the bottle.
The method of the water-fast-latex emulsion that bleaches that is provided for pressure sensitive adhesive is disclosed in the prior art.United States Patent (USP) 5,286,843 disclose by remove water soluble ion and with pH regulator to about at least 6 methods of improving the water-whitening resistance of the pressure sensitive adhesive that comprises aqueous latex emulsion and water soluble ion.This patent disclosure water soluble ion can remove by many technology, comprise centrifugal, dialysis, precipitation and spent ion exchange resin deionization.The preferred method of removing water soluble ion is that the pressure sensitive adhesive that comprises aqueous emulsion of aqueous latex emulsion, preparation or both are contacted with ion exchange resin.International publication WO 97/11996A 1 discloses the method for the latex emulsion that is used to prepare the heat-resisting water that can be used for contact adhesive composition-bleach.This method comprises a kind of monomer mixture of copolymerization, and it comprises at least a water miscible comonomer of part that comprises the alkyl acrylate of the alcohol of at least 4 carbon atoms, at least a polar comonomers and at least a amount for about at least 7 weight %.Be aggregated at least a nonionogenic tenside that comprises at least 8 moles of ethylene oxide and at least aly comprise at most that the anion surfactant of about 10 moles of ethylene oxide carries out under existing.With polymerization product neutralization, produce pH and be higher than 7 and comprise the emulsion of the particle of high about 165nm of volume average particulate size diameter.After polymerization, can add ionogen to stablize from the opacity of the film of this emulsion curtain coating.International publication WO00/61670 discloses the method that is used to prepare the aqueous latex emulsion that is used for pressure sensitive adhesive, and this pressure sensitive adhesive can also keep binding property in the hot water environment except that the water-whitening resistance with raising.This method comprises from a kind of monomer mixture and prepares the aqueous latex emulsion, this mixture is gone up composed of the following components substantially: at least a have the alkyl acrylate of at least 4 carbon atoms, at least a ethylenically unsaturated carboxylic acids and an at least a styrene monomer in alkyl chain, and this is aggregated at least a anion surfactant and oxidation-reduction type free radical initiator system and carries out under existing.According to the aqueous latex emulsion of the method for WO 00/61670 preparation,, has the polymer particle that the average particulate size diameter is less than or equal to about 100nm according to open.The central none of above-mentioned patent/publication discloses the use polymerizable surfactants and has prepared pressure sensitive adhesive.
United States Patent (USP) 5,928,783 and 6,239,240 disclose the method for preparing the aqueous emulsion polymkeric substance that can be used for pressure sensitive adhesive.This polymkeric substance prepares by reacting at least a ethylenically unsaturated monomer and having terminal allylamine polymerizable surfactants partly.This patent does not openly have the preparation of pressure sensitive adhesive of the water-whitening resistance of raising.
Summary of the invention
An object of the present invention is to provide pressure sensitive adhesive (" the PSA ") composition of water-whitening resistance with raising.Another object of the present invention provides the method for the pressure sensitive adhesive for preparing the water-whitening resistance with raising.
The present invention has realized the purpose of these and other.To carry out nonrestrictive description to the present invention hereinafter.
According to the present invention, the method for preparing the pressure sensitive adhesive of the water-whitening resistance with raising is provided, it comprises: (a) form polymerisable moisture pre--emulsion, it comprises: (i) alkyl acrylate of at least a hydrophobic alcohol or alkyl methacrylate, at least a hydrophilic monomer of (ii) about at least 1 weight %, the alkyl acrylate or the alkyl methacrylate of the hydrophilic alcohol of at least a part of (iii) about at least 5 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer (i) in this pre--emulsion, (ii) and gross weight (iii); (b) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from compound, the phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether or its mixture with terminal allylamine part; (c) continuously pre--emulsion is joined in the mixture of (b), makes pre--letex polymerization form latex emulsion, wherein in advance-add additional polymerization starter between the polymerization period of emulsion; (d) with the pH of suitable alkali adjusting latex emulsion, making pH is about 6.5 to about 9; Wherein, the significant quantity of the polymerisable surfactant of water-soluble or water dispersible is to produce the necessary amount of pressure sensitive adhesive that average particulate size is less than or equal to 200nm in the mixture of (b).
In addition, according to the present invention, provide the method for preparing the pressure sensitive adhesive of the water-whitening resistance with raising, it comprises:
(a) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from compound, the phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether or its mixture with terminal allylamine part; (b) in this mixture, add monomer and randomly additional water continuously, with the resulting emulsion of polymerization to form latex emulsion, wherein during this letex polymerization, add additional polymerization starter, comprise with wherein said monomer: (i) alkyl acrylate of at least a hydrophobic alcohol or alkyl methacrylate, at least a hydrophilic monomer of (ii) about at least 1 weight %, the alkyl acrylate or the alkyl methacrylate of the hydrophilic alcohol of at least a part of (iii) about at least 5 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer (i), (ii) and gross weight (iii); (c) with the pH of suitable alkali adjusting latex emulsion, making pH is about 6.5 to about 9; Wherein, the significant quantity of the polymerisable surfactant of water-soluble or water dispersible is to produce the necessary amount of pressure sensitive adhesive that average particulate size is less than or equal to 200nm in mixture.
In addition, according to the present invention, the contact adhesive composition of the water-whitening resistance with raising is provided, it comprises the aqueous emulsion polymkeric substance, described polymkeric substance comprises the polyreaction product of polymerisable aqueous emulsion, this polymerisable aqueous emulsion comprises: (i) alkyl acrylate of at least a hydrophobic alcohol or alkyl methacrylate, at least a hydrophilic monomer of (ii) about at least 1 weight %, the alkyl acrylate or the alkyl methacrylate of the hydrophilic alcohol of at least a part of (iii) about at least 5 weight %, (iv) water-soluble or water dispersible polymerisable surfactant, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer (i), (ii) and gross weight (iii); The pH of wherein said polymkeric substance after described polymerization, be adjusted to pH be about 6.5 to about 9 and the average particulate size of described polymkeric substance be less than or equal to 200nm.
Further, according to the present invention, provide pressure sensitive adhesive by the water-whitening resistance with raising of aforesaid method production.
Randomly, method of the present invention be included in monomer (i), (ii) and transformation efficiency (iii) be higher than after 90%, in latex emulsion, add C
2To C
10The vinyl ester of carboxylic acid.The present invention also randomly provides pressure sensitive adhesive, wherein said polyreaction product also be included in monomer (i), (ii) and transformation efficiency (iii) be higher than the C that joins after 90% in the polyreaction product
2To C
12The vinyl ester of carboxylic acid.
Description of drawings
Describing when of the present invention, will be with reference to figure 1, it has shown directly-and the pressure sensitive adhesive of the present invention (curve 1 and 2) of transfers-coatings and contrast pressure sensitive adhesive (curve 3) that the use conventional surfactants prepares in the variation of 24 hour time internal absorbance.
Detailed Description Of The Invention
The invention provides the aqueous emulsion pressure sensitive adhesive, it can be used for producing for example label, applique or the like product, translucent especially at least and label that contacts water or high humidity during use and applique plane materiel.Pressure sensitive adhesive of the present invention especially can be used for bottle label to be used, wherein labelled bottle contact hot water environment.
Pressure sensitive adhesive of the present invention has the water-whitening resistance of raising.The degree of water-bleach can be measured on vision ground, perhaps measures by means of the ultraviolet spectroscopy and measures as the absorbancy of the function of time.At this, PSA of the present invention is considered to have acceptable PSA film when having following feature the water level that bleaches: (a) after room temperature water logging in 24 hours the increase of (when measuring) absorbancy by means of the ultraviolet spectroscopy less than 0.2, preferably less than 0.05, and/or (b) in 190 (87.8 ℃) water dipping do not have visible to change after 30 minutes.
First embodiment of the present invention relates to the method for the pressure sensitive adhesive for preparing the water-whitening resistance with raising, and it comprises:
(a) form polymerisable moisture pre--emulsion, it comprises: (i) alkyl acrylate of at least a hydrophobic alcohol or alkyl methacrylate, at least a hydrophilic monomer of (ii) about at least 1 weight %, the alkyl acrylate or the alkyl methacrylate of the hydrophilic alcohol of at least a part of (iii) about at least 5 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer (i) in this pre--emulsion, (ii) and gross weight (iii); (b) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from compound, the phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether or its mixture with terminal allylamine part; (c) continuously pre--emulsion is joined in the mixture of (b), makes pre--letex polymerization form latex emulsion, wherein in advance-add additional polymerization starter between the polymerization period of emulsion; (d) with the pH of suitable alkali adjusting latex emulsion, making pH is about 6.5 to about 9; Wherein the significant quantity of the polymerisable surfactant of water-soluble or water dispersible is to produce average particulate size to be less than or equal to 200nm, preferably to be less than or equal to the necessary amount of pressure sensitive adhesive of 100nm in the mixture of (b).
Second embodiment of the present invention relates to the method for the pressure sensitive adhesive for preparing the water-whitening resistance with raising, and it comprises:
(a) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from compound, the phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether or its mixture with terminal allylamine part; (b) in this mixture, add monomer and randomly additional water continuously, with the resulting emulsion of polymerization to form latex emulsion, wherein during this letex polymerization, add additional polymerization starter, comprise with wherein said monomer: (i) alkyl acrylate of at least a hydrophobic alcohol or alkyl methacrylate, at least a hydrophilic monomer of (ii) about at least 1 weight %, the alkyl acrylate or the alkyl methacrylate of the hydrophilic alcohol of at least a part of (iii) about at least 5 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on the monomer (i) that joins in the described mixture, (ii) and gross weight (iii); (c) with the pH of suitable alkali adjusting latex emulsion, making pH is about 6.5 to about 9; Wherein the significant quantity of the polymerisable surfactant of water-soluble or water dispersible is to produce average particulate size to be less than or equal to 200nm, preferably to be less than or equal to the necessary amount of pressure sensitive adhesive of 100nm in mixture.
According to operable hydrophobic acrylic acid's alkyl ester of the present invention or alkyl methacrylate monomer comprise the alkyl acrylate or the alkyl methacrylate of alcohol, the moieties of wherein said alcohol be straight or branched and comprise at least 4 carbon atoms.The alkyl group of alkyl acrylate or alkyl methacrylate monomer preferably has 4 to about 14 carbon atoms, more preferably 4 to about 10 carbon atoms with most preferably 4 to the straight or branched alkyl of about 8 carbon atoms.The monomeric example of this class comprises, but be not limited to, Isooctyl acrylate monomer, vinylformic acid 4-methyl-2-pentyl ester, vinylformic acid 2-methyl-butyl ester, vinylformic acid isopentyl ester, sec-butyl acrylate, n-butyl acrylate, 2-EHA, isodecyl methacrylate, vinylformic acid ester in the different ninth of the ten Heavenly Stems, isodecyl acrylate or the like, they can be individually or use with two or more mixture.
At present preferred hydrophobic monomer is 2-EHA, n-butyl acrylate and composition thereof.
The amount of hydrophobic acrylic acid's alkyl ester or alkyl methacrylate monomer based on monomer (i), (ii) and gross weight (iii) be that preferably approximately 70 is to about 90 weight % and more preferably about 75 to about 85 weight %.
According to the operable hydrophilic monomer of the present invention is copolymerizable and be water miscible monomer with hydrophobic monomer.This hydrophilic monomer is selected from monoene monocarboxylic acid, monoene dicarboxylic acid or its mixture.
The example of the hydrophilic monomer that is fit to includes but are not limited to vinylformic acid, methacrylic acid, fumaric acid, toxilic acid, methylene-succinic acid, Ba Dousuan, oligomeric acrylic acid and composition thereof.At present preferred acid is vinylformic acid, methacrylic acid and composition thereof.
The amount of hydrophilic monomer based on monomer (i), (ii) and gross weight (iii) be about at least 1 weight %, preferably approximately 2 to about 10 weight %, more preferably about 3 to about 10 weight % and most preferably about 4 to about 8 weight %.
Comprise pure alkyl acrylate or alkyl methacrylate according to hydrophilic alkyl acrylate of the operable part of the present invention or alkyl methacrylate monomer, the moieties of wherein said alcohol has 1 to 2 carbon atom.The hydrophilic monomer of part can also be called as the water miscible monomer of part.
The hydrophilic monomeric example of part that is fit to comprises methyl acrylate, methyl methacrylate, ethyl propenoate and composition thereof.At present preferred acid is methyl acrylate, methyl methacrylate and composition thereof, and methyl acrylate is most preferred at present.
The hydrophilic monomeric amount of part based on monomer (i), (ii) and gross weight (iii) be about at least 5 weight %, preferably approximately 5 to about 20 weight %, more preferably about 5 to about 18 weight % and most preferably about 10 to about 16 weight %.
Comprise United States Patent (USP) 5 according to the operable water-soluble or water dispersible polymerizable surfactants of the present invention with terminal allylamine part, 928,783 and United States Patent (USP) 6,239,240 those disclosed polymerizable surfactants, it is hereby incorporated by in full.Preferably, polymerisable surfactant of the present invention comprises hydrophilic part and hydrophobic parts, described hydrophilic part is selected from sulfonate allylamine part, vitriol allylamine part or phosphoric acid salt allylamine part and described hydrophobic parts is selected from-R, perhaps has general formula R O-(CH
2CH
2O)
n-group; Wherein R is alkyl group or alkyl-alternate phenyl, and wherein alkyl group has 1 to 20 carbon atom, and preferred 10 to 18 carbon atoms and n are 2 to 100 integers, preferred 2 to 15.Hydrophilic part is connected by covalent linkage with hydrophobic parts.The mixture of this class polymerizable surfactants can be used for preparing polymkeric substance of the present invention.Can be used for the water-soluble or water dispersible polymerizable surfactants with terminal allylamine part of the present invention can obtain from Stepan company by Polystep NMS trade mark.
Water-soluble or the water dispersible polymerisable surfactant with terminal allylamine part that is fit to includes but are not limited to following example.
Preferred polymerizable surfactants is the allyl amine salt with alkyl benzene sulphonate (ABS) of following general formula:
R wherein
1Be alkyl group with 1 to 20 carbon atom, preferred 10 to 18 carbon atoms, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.X
+Preferably
+NH
3The example of this class polymerizable surfactants is the allyl amine salt of Witco 1298 Soft Acid.
Another kind of preferred polymerizable surfactants is the alkyl oxide sulfuric acid allyl amine salt with following general formula:
R wherein
2Be the alkyl group with 1 to 20 carbon atom, preferred 10 to 18 carbon atoms, n is 2 to 100, preferred 2 to 15 integer, and X
+Be selected from NH
3+,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.X
+Preferably
+NH
3The example of this class polymerizable surfactants is lauryl ether (laureth) vitriolic allyl amine salt.
Another kind of preferred polymerizable surfactants is the phosphoric acid ester allyl amine salt with following general formula:
R wherein
3Be the phenyl of alkyl or alkyl-replacement, wherein this alkyl group has 1 to 20 carbon atom, and n is 2 to 100, preferred 2 to 15 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.X
+Preferably
+NH
3The example of this class polymerizable surfactants is the allyl amine salt of nonyl phenol ethoxylate (9 moles of EO) phosphoric acid ester.
Another kind of preferred polymerizable surfactants is the sulfuric acid allyl amine salt with following general formula:
R
6-SO
3 -+X-CH
2-CH＝CH
2
R wherein
6Be alkyl group with 6 to 20 carbon atoms, preferred 10 to 18 carbon atoms, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.X
+Preferably
+NH
3
Can comprise being disclosed in United States Patent (USP) 5,332 as the phenyl compound of the replacement with at least one alkenyl substitutents of water-soluble or water dispersible polymerizable surfactants according to the present invention, those in 854, it draws at this in full and is reference.
The phenyl compound of the replacement with at least one alkenyl substitutents that is fit to comprises the compound with following general formula:
Wherein, R
7Be alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
8Be hydrogen atom or alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
9Be hydrogen atom or propenyl group; A is the alkylidene group with 2 to 4 carbon atoms unsubstituted or that replace; N is 1 to about integer of 200, preferred 2 to about 100; With M be basic metal, ammonium ion or alkanolamine residue.
In the phenyl compound that the present invention replaces, R
7And R
8Alkyl, alkenyl and aralkyl select independently, and can be identical or different.The alkyl group that is fit to includes but are not limited to hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.The kiki alkenyl group that is fit to comprises, but be not limited to hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base and vaccenic acid base.The aralkyl that is fit to includes but are not limited to styryl, benzyl and cumyl.
The propenyl group can be used as trans and cis-isomeride exists.For the purposes of the present invention, these isomer can use or use as mixture independently.
For A, suitable alkylidene group unsubstituted or that replace comprises for example ethylidene, propylidene, butylidene and isobutylene.The poly suboxygen alkyl group-(AO)
n-can be homopolymerization, block or unregulated polymer or its mixture.
The condition of reaction that is used to produce the phemyol surface active agent of replacement of the present invention is not crucial.For example, the phemyol surface active agent that replaces can be by for example oxyethane (EO) or propylene oxide (PO) add on the alkylating propenyl phenol with alkylene oxide in common mode, with sulfating agent these affixtures of sulfation such as sulfuric acid, thionamic acid, chlorsulfonic acid for example, then with in the alkaline matter and produce.
The phenyl compound that an at present preferred class replaces is those compounds with following general formula:
Wherein, R
7, A, M and n such as above-mentioned definition.Preferred compound is R wherein
7Be alkyl, A is ethylidene (CH
2CH
2-) and M be those of basic metal or ammonium.Most preferred is that wherein M is an ammonium, R
7Be that nonyl and n are those of about 10 to about 30, for example can be from Dai-Ichi Kogyo Seiyaku Co., the compound that Ltd. (Tokyo, Japan) obtains with trade name Hitenol BC.
Can comprise Japanese Patent JP2596441B2 (Dai-Ichi Kogyo Seiyaku Co., Ltd.) those disclosed as poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether compound water-soluble or the water dispersible polymerizable surfactants according to the present invention.
Poly suboxygen alkyl-1-(allyloxy methyl) the sulfated alkyl ether compound that is fit to comprises the compound with following general formula:
Wherein, R
10Be to comprise 8 to 30 carbon atoms, preferred 8 to 14 carbon atoms and the more preferably straight or branched alkyl group of 10 to 12 carbon atoms; R
11Be hydrogen or methyl, preferred hydrogen; A is the alkylidene group with 2 to 4 carbon atoms unsubstituted or that replace; N is 0 or 1 to about 200, preferred 2 to about integer of 100, more preferably 2 to about 30; With M be basic metal, ammonium ion or alkanolamine residue.The example of alkanolamine residue comprises monoethanolamine, trolamine or the like.
For A, suitable alkylidene group unsubstituted or that replace comprises for example ethylidene, propylidene, butylidene and isobutylene.The poly suboxygen alkyl group-(AO)
n-can be homopolymerization, block or unregulated polymer or its mixture.
Poly suboxygen alkyl-1-of the present invention (allyloxy methyl) sulfated alkyl ether compound can be according to the method preparation of describing among the Japanese Patent JP 2596441B2.
A preferred class poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether compound is those compounds with following general formula at present:
R wherein
10It is the alkyl group that comprises 8 to 14 carbon atoms and preferred 10 to 12 carbon atoms; N is 1 to about 200, preferred 2 to about integer of 100, more preferably 2 to about 30; With M be basic metal, ammonium ion or alkanolamine residue.Preferred compound is R wherein
10Be decyl or dodecyl group, n be 5 to 10 and M be NH
4Those, for example can be from Dai-Ichi KogyoSeiyaku Co., the compound that Ltd. (Tokyo, Japan) obtains with trade mark Hitenol KH.
Be used for this method, for example in the step (a) of this method with the total amount of the water-soluble or water dispersible polymerizable surfactants that (b) adds, based on monomer (i), (ii) and gross weight (iii), for about 0.1 to about 5 weight %, preferably approximately 0.5 to about 2 weight %.
Joining the amount of the water-soluble or water dispersible polymerizable surfactants in the mixture of water, polymerizable surfactants and polymerization starter, is can produce effectively to have average particulate size and be less than or equal to 200nm, preferably be less than or equal to the amount of latex emulsion of the particle of 100nm.The significant quantity that the particle size that preparation requires needs depends on as known in the art particle size to be had the operational condition of influence, comprises stirring (shearing), viscosity or the like.The remainder of polymerizable surfactants is with monomer (i), (ii) and (iii) add.In the preferred embodiment of the invention, the amount that joins the polymerizable surfactants in the mixture of water, polymerizable surfactants and polymerization starter is in step (a) and about at least 20 weight % of the total amount of the polymerizable surfactants that adds (b).In the preferred embodiment of the invention, with the amount of monomer (i), the polymerizable surfactants that (ii) and (iii) adds account in step (a) and (b) total amount of the polymerizable surfactants of adding less than about 80 weight %.
The inventive method is also used at least a water miscible polymerization starter.Can use the water-soluble polymerization initiator of any routine of the letex polymerization that is applicable to acrylate monomer usually, and this class polymerization starter is well known in the art.The concentration of typical water-soluble polymerization initiator based on the monomer (i) that is fed to pre--emulsion, (ii) and gross weight (iii) be that about 0.01 weight % is to about 1 weight %, preferably approximately 0.01 weight % to about 0.5 weight %.Water-soluble polymerization initiator can use separately or be used in combination with one or more conventional reductive agents, for example hydrosulphite, metabisulphite, xitix, sodium formaldehyde sulphoxylate, ferrous sulfate, ferrous ammonium sulphate, ethylenediamino tetraacetic acid iron (ferricethylenediamine-tetraacetic acid) or the like.Comprise water miscible persulphate, superoxide, azo-compound or the like and composition thereof according to the operable water-soluble polymerization initiator of the present invention.The example of water soluble starter comprises, but be not limited to, persulphate (for example Potassium Persulphate and Sodium Persulfate), superoxide (for example hydrogen peroxide and tert-butyl hydroperoxide) and azo-compound (for example 4,4 '-azo two (4-cyano group-valeric acid) is from the V-501 of WakoChemicals).At present preferred water-soluble polymerization initiator is a persulphate, especially Potassium Persulphate.
Polymerization can cause by any ordinary method well known by persons skilled in the art, for example by heating or apply radiation.Initiating method depends on the water-soluble polymerization initiator of use, and this is conspicuous to those skilled in the art.
Water-soluble polymerization initiator can any routine known in the art mode add polyreaction.Preferably a part of initiator is joined in the initial reactor charging at present, it comprises the polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk.The remainder of initiator can be during letex polymerization continuously or increment ground add.At present preferred increment ground adds remaining initiator.
After polymerization, the pH of latex emulsion is by making latex emulsion and making pH bring up to about 6.5 alkali that are fit to about 9, preferably approximately 7 to about 8 necessary amounts to contact and regulate.The example of the alkali that is fit to that is used to regulate the pH of latex emulsion comprises alkali metal hydroxide, alkaline earth metal hydroxides, ammoniacal liquor, amine or the like and composition thereof.Present alkali preferred for the present invention is ammoniacal liquor.
Latex emulsion has about 40 solids contents to about 70 weight %, preferably approximately 45 to about 55 weight % and more preferably about 46 to about 48 weight % usually.
Choose wantonly in the present invention, but be in the embodiment preferred at present, the inventive method also is included in monomer (i), (ii) and transformation efficiency (iii) is higher than 90%, preferably be higher than 95% and more preferably be higher than after 97%, adds C in latex emulsion
2To C
12The vinyl ester of aliphatic carboxylic acid.Usually, in the methods of the invention, this can be by finishing monomer (i), (ii) and after the adding (iii), adding vinyl ester and finish in latex emulsion.
The example that is used for the vinyl ester that is fit to of the inventive method comprises, but be not limited to, the vinyl ester of vinyl acetate, propionate, vinyl butyrate, isopropylformic acid vinyl acetate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate, new-acid (can trade mark VeoVa
TMObtain from Resolution Performance Products), or the like, and composition thereof.Preferred vinyl ester is to have those of the reactive behavior that is similar to water-soluble or water dispersible polymerizable surfactants.
The amount that joins the vinyl ester in the latex emulsion is based on joining monomer (i) in the polymerization, (ii) and gross weight (iii) is about 0.1 to about 1 weight %, preferably approximately 0.2 to about 0.8 weight %.
If vinyl ester is used for the inventive method, preferably additional polymerization starter is added when adding vinyl ester at present.
Polyreaction can be carried out in the reaction vessel that can carry out letex polymerization of any routine.
Polymerization can be carried out under the temperature that typically is used for letex polymerization.Polymerization is preferably carried out under about 85 ℃ temperature for 60 ℃ at about 50 ℃ to about 95 ℃, preferably approximately.
Polymerization time is the needed time of transformation efficiency that for example reaches hope at other reaction conditions, for example temperature variation form and reactive component on the basis of monomer, initiator or the like.Polymerization time is conspicuous to those skilled in the art.
The 3rd embodiment of the present invention relates to the contact adhesive composition of the water-whitening resistance with raising, it comprises the aqueous emulsion polymkeric substance, described polymkeric substance comprises the polyreaction product of polymerisable aqueous emulsion, this polymerisable aqueous emulsion comprises: (i) alkyl acrylate of at least a hydrophobic alcohol or alkyl methacrylate, at least a hydrophilic monomer of (ii) about at least 1 weight %, the alkyl acrylate or the alkyl methacrylate of the hydrophilic alcohol of at least a part of (iii) about at least 5 weight %, (iv) water-soluble or water dispersible polymerisable surfactant, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer (i), (ii) and gross weight (iii); The pH of wherein said polymkeric substance after described polymerization, be adjusted to pH be about 6.5 reach about 9 and the average particulate size of described polymkeric substance be less than or equal to 200nm, preferably be less than or equal to 100nm.
Choose wantonly in the present invention, but be in the embodiment preferred at present, PSA composition of the present invention also is included in monomer (i), (ii) and transformation efficiency (iii) is higher than 90%, preferably be higher than 95% and more preferably be higher than after 97% C that adds in latex emulsion
2To C
12The vinyl ester of aliphatic carboxylic acid.
Embodiment
The abbreviation of material and source
2-EHA: 2-EHA; Ashland Inc.
BA: butyl acrylate; Ashland Inc.
MA: methyl acrylate; Ashland Inc.
IOA: isooctyl acrylate ester; Ashland Inc.
MMA: methyl methacrylate; Ashland Inc.
AA: vinylformic acid; Ashland Inc.
MAA: methacrylic acid; Ashland Inc.
Polystep NMS-7: lauryl ether-3-sulfuric acid allyl-ammonium; Stepan Company
Polystep NMS-5: myrceane sulfuric acid allyl-ammonium; Stepan Company
Hitenol BC-2020: 20% active substance in water, n are about 20;
Dai-Ichi?Kogyo?Seiyaku?Co.，Ltd.
VeoVa5: PIVALIC ACID CRUDE (25) vinyl ester; Resolution Performance Products
PPS: Potassium Persulphate; Sigma-Aldrich Co.
NH
4OH: ammoniacal liquor (28%); Sigma-Aldrich Co.
Abex EP-120: sulfation Nonylphenoxy-poly-(ethyleneoxy group) ethanol; Rhodia
AOT-75: dioctyl sodium sulfo-succinate; Cytec
Igepal Co-630: nonyl phenol ethoxylate (having 9 moles of ethylene oxide); Rhodia
Mylar: polyester film; DuPont
Poly H9: release liner; Rexam Release
Hitenol KH-05: poly suboxygen ethyl-1-(allyloxy methyl) sulfated alkyl ether, ammonium salt; Dai-Ichi Kogyo Seiyaku Co., Ltd.
Embodiment 1
In being equipped with the 2L jacketed glass reactor of reflux exchanger, thermopair and two paddle agitators, the polyacrylic ester latex of preparation 701.5g.Monomer is pre--and emulsion prepares by mixing following material: the Polystep NMS-7 of the MAA of MA, the 6.25g of the 2-EHA of 110g water, 192.4g, the BA of 64g, 45g and the AA of 9.75g and 9.27g.The Polystep NMS-7 of 140g water and 3g packs in reactor.Individually, the PPS stock solution (0.94 weight % concentration) of preparation 117g in water.Water heats this reactor.When temperature reaches 79 ℃, add the PPS of 0.75g, then with the speed of 2.1-2.2g/min add continuously monomer pre--emulsion 3.5hr.Temperature maintenance at 83 ℃, and is stirred this polymerization charging continuously under 240rpm.PPS stock solution with 10g added reactor in per 20 minutes.After the adding of having finished pre--emulsion, temperature of reactor is elevated to 85 ℃ and stirred other 40 minutes, in reactor, add the VeoVa5 of 1.5g and the PPS stock solution of 5g then.
This latex has 47.2% solid.The mensuration of solid weight % is as follows: the latex of known quantity is put in the aluminium gravimetric tank of weighing, and drying is 60 minutes under 150 ℃, weigh once more this jar and calculating solids content.When using Horiba laser light scattering particle size distribution analyzer LA-910 type to measure, average particulate size is 80nm.When using Orion 250 model pH meter to measure, pH is 2.34.Use Brookfield viscometer LV II+, the brookfield viscosity that uses axle #3 to measure under 30rpm is 860cp.
Use NH then
4OH is 7.85 with the latex pH that neutralizes.
Directly be coated in neutral latex on the 1 mil polyester film and on the Poly H9 release liner.With two membrane air dryers 10 minutes, then 90 ℃ of following heat dryings 5 minutes.With the polyester film that applies with release liner laminated (directly applying) with the release liner and polyester film laminated (transfer coating) that apply.Bleach/water soaking test for water, this release liner is removed, thereby make polymer surfaces be exposed to water.Use the ultraviolet spectroscopy (UV/VIS) of Cintra 40 ultraviolet-visible spectrophotometers to be used to measure absorbancy.The polyester film (plane materiel) that applies is placed the cuvette that water is housed in time=0 o'clock.Measure and write down the absorbancy 24hr (room temperature) under the 400nm.Directly-and the final absorbancy of transfer-coated film increase and be respectively 0.015 and 0.041 (the curve #1 and 2 among Fig. 1).
Embodiment 2 (contrast)
In control experiment, prepare latex according to the program of describing among the embodiment 1, substitute Polystep NMS-7 except using conventional tensio-active agent.Therefore, the Igepal Co-630 that 5.3g Abex EP-120 (30% solid) is used for the AOT 75 of Abex EP-120,0.78g of the reinforced and 3.2g of initial reactor and 3.88g be used to stable should pre--emulsion.Average particulate size, 46.9% solid, pH=2.24 and brookfield viscosity that final latex has 87nm are 546.With this latex pH7.84 that neutralizes.As direct coating latex film as described in the embodiment 1, and in room temperature water in 24hr dip test period detecting ultraviolet/visible absorbance.Final absorbancy is 0.388 (the curve #3 among Fig. 1).
Embodiment 1 and 2 result show that PSA of the present invention has significantly improved water-whitening resistance with the polymer phase ratio of similar use conventional surfactants preparation.
Embodiment 3
Carry out polymerization according to the program of describing in the experiment 1, except replacing 2-EHA, with the iOA of BA, MA, AA and MAA emulsification 192 grams.
This latex has 47.5% solid.Average particulate size is 98nm and pH=2.23.Brookfield viscosity is 740cp.Use NH
4OH is 7.98 with this latex pH that neutralizes.
By on polyester film, preparing latex film with direct coating of 1 mil coated weight.Absorbancy is changed to 0.039 after 24hr room temperature dipping.
Embodiment 4
Carry out polymerization according to the program of describing in the experiment 1, except restrain MA emulsifications 16 gram AA with 192 gram 2-EHA, 64 gram BA and 45.That describes among polymerizing condition and the embodiment 1 is identical.This latex has 45.4% solid, and pH=2.38 and brookfield viscosity are 572.Average particulate size is 77nm.Use NH
4OH is 7.8 with this latex pH that neutralizes.
Having 0.046 absorbancy at the direct coated film on the polyester film after the water soaking test of 24hr room temperature increases.
Embodiment 5
Carry out polymerization according to the program of describing in the experiment 1, except MMA with 2-EHA, BA, AA and MAA emulsification 45 grams of description amount.This latex has 45.91% solid, and pH=2.41 and brookfield viscosity are 678.Average particulate size is 93nm.With this latex NH
4The OH pH=7.95 that neutralizes.
As described in embodiment 1, bleach by on polyester film, directly applying preparation latex film and test water.The absorbancy increase is 0.024 after the 24hr in room temperature water.
Embodiment 6 (contrast)
Carry out polymerization according to the program of describing in the experiment 1, except not using the water miscible monomer of part, i.e. methyl acrylate or methyl methacrylate.Therefore, this pre--emulsion is by forming with 12.9 gram Polystep NMS-7 emulsive, 217 gram 2-EHA, 84 gram BA, 6.4 gram MAA and 9.1 gram AA in 110 gram water.This latex has 46% solid, and pH=2.39 and brookfield viscosity are 380.Average particulate size is 106nm.
Use NH
4OH is with this latex pH=7.98 that neutralizes.
Latex film directly is coated on the polyester film.The increase of the absorbancy of latex film is 0.38 after the water logging of 24hr room temperature.
The result of embodiment 6 shows, the PSA that produces without the polymerization of portion water soluble monomers has unacceptable water character that bleaches.
Embodiment 7 (contrast)
Carry out polymerization according to the program of describing in the experiment 1, except in initial reactor is reinforced, adding the Polystep NMS-7 of 1 gram.
This latex has 47.1 solids, and pH=2.76 and brookfield viscosity are 348cp.Average particulate size is 119nm.With this latex NH
4Neutralize pH=7.54 and directly being coated on the polyester film of OH.The absorbancy increase is 0.13 after the water logging of 24hr room temperature.
The result of embodiment 7 shows, use is less than PSA that the polymerizable surfactants of significant quantity produces and has unacceptable water character that bleaches in initial reactor is reinforced, and particle has excessive average particulate size.
Embodiment 8
Carry out polymerization according to the program of describing in the experiment 1,, in initial reactor is reinforced, add the Polystep NMS-5 of 4.33 grams except replacing adding the PolystepNMS-7 of 3 grams.Equally, this monomer mixture with 17.9 the gram Polystep NMS-5 emulsifications.This latex has 46.5% solid.Particle size is 78nm, pH=2.64.With this latex NH
4The OH pH=7.49 that neutralizes, and directly be coated on the polyester film.
The absorbancy increase is 0.05 after room temperature water soaking test in 24 hours.
Embodiment 9
In being equipped with the 2L jacketed glass reactor of reflux exchanger, thermopair and two paddle agitators, the preparation polyacrylic ester latex.In independent container, by mix following material prepare monomer pre--emulsion: the Hitenol BC-2020 of the MAA of MA, the 10.06g of the 2-EHA of 122.8g water, 298g, the BA of 99.1g, 69.75g and the AA of 14.08g and 14.75g.The PPS of 296.72g water, 1.18g and the Hitenol BC-2020 of 7.37g pack in reactor.Individually, the PPS stock solution (0.94 weight % concentration) of preparation 61.77g in water.Water heats this reactor.When temperature reaches 79 ℃, with the speed of 3g/min begin monomer pre--continuous charging of emulsion, and continued 200 minutes.Temperature maintenance at 83 ℃, and is stirred this polymerization charging continuously under 240rpm.Pre--emulsions of 200 minutes in the joining day, in advance-after emulsion begins to add 20 minutes, in reactor, added the 6gPPS stock solution in per 20 minutes.In advance-emulsion add finish after, temperature of reactor is elevated to 88 ℃ and stirred other 60 minutes.
This latex has 46.79% solid.The mensuration of solid weight % is as follows: the latex of known quantity is put in the aluminium gravimetric tank of weighing, and drying is 60 minutes under 150 ℃, weigh once more this jar and calculating solids content.When using Horiba laser light scattering particle size distribution analyzer LA-910 type to measure, average particulate size is 86nm.When using Orion 250 model pH meter to measure, pH is 2.34.Use Brookfield viscometer LV II+, the brookfield viscosity that uses axle #3 to measure under 30rpm is 1124cp.
Use NH then
4OH is 7.85 with the latex pH that neutralizes.
Neutral latex directly is coated on the 1 mil polyester film.With this membrane air dryer 10 minutes, then 90 ℃ of following heat dryings 5 minutes.Polyester film and release liner laminated (directly applying) with this coating.Bleach/water soaking test for water, this release liner is removed, thereby make polymer surfaces be exposed to water.Use the ultraviolet spectroscopy (UV/VIS) of Cintra 40 ultraviolet-visible spectrophotometers to be used to measure absorbancy.The polyester film (plane materiel) that applies is placed the cuvette that water is housed in time=0 o'clock.Measure and write down the absorbancy 24hr (room temperature) under the 400nm.Directly-and it is 0.005 that the final absorbancy of coated film increases, it is equivalent to 98.8% transmittance.
Embodiment 10
In being equipped with the 2L jacketed glass reactor of reflux exchanger, thermopair and two paddle agitators, the preparation polyacrylic ester latex.In independent container, by mix following material prepare monomer pre--emulsion: the Hitenol KH-05 of the MAA of MA, the 9.1g of the 2-EHA of 134.5g water, 271.9g, the BA of 90.7g, 63.6g and the AA of 12.9g and 5.4g.The PPS of 364.4g water, 1.57g and the Hitenol KH-05 of 1.35g pack in reactor.Individually, the PPS stock solution (2.5 weight % concentration) of preparation 35.5g in water.Water heats this reactor.When temperature reaches 79 ℃, with the speed of 2.94g/min begin monomer pre--continuous charging of emulsion, and continued 200 minutes.Temperature maintenance at 83 ℃, and is stirred this polymerization charging continuously under 240rpm.Pre--emulsions of 200 minutes in the joining day, in advance-after emulsion begins to add 20 minutes, in reactor, added the 3.5gPS stock solution in per 20 minutes.In advance-emulsion add finish after, temperature of reactor is elevated to 88 ℃ and stirred other 60 minutes.This latex has 45.8% solid.The mensuration of solid weight % is as follows: the latex of known quantity is put in the aluminium gravimetric tank of weighing, and drying is 60 minutes under 150 ℃, weigh once more this jar and calculating solids content.When using Horiba laser light scattering particle size distribution analyzer LA-910 type to measure, average particulate size is 76nm.When using Orion 250 model pH meter to measure, pH is 2.2.Use Brookfield viscometer LV II+, the brookfield viscosity that uses axle #3 to measure under 30rpm is 1200cp.
Use NH then
4OH this latex that neutralizes is 7.12 to pH.
Neutral latex directly is coated on the 1 mil polyester film.With this membrane air dryer 10 minutes, then 90 ℃ of following heat dryings 5 minutes.Polyester film and release liner laminated (directly applying) with this coating.Bleach/water soaking test for water, this release liner is removed, thereby make polymer surfaces be exposed to water.Use the ultraviolet spectroscopy (UV/VIS) of Cintra 40 ultraviolet-visible spectrophotometers to be used to measure absorbancy.The polyester film (plane materiel) that applies is placed the cuvette that water is housed in time=0 o'clock.Measure and write down the absorbancy 24hr (room temperature) under the 400nm.Directly-it is 0.014 that the final absorbancy of coated film increases.Equally tackiness agent is exposed in 190 water 10 minutes.After high temperature exposure, there is not visible color change.
Claims (118)
1. prepare the method for the pressure sensitive adhesive of the water-whitening resistance with raising, it comprises:
(a) form polymerisable moisture pre--emulsion, it comprises: (i) (methyl) vinylformic acid C of at least a hydrophobic alcohol
4-14Alkyl ester, the (ii) at least a hydrophilic monomer of 2-10 weight %, (iii) (methyl) vinylformic acid C of the hydrophilic alcohol of at least a part of 5-20 weight %
1-2Alkyl ester, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on described pre--monomer (i) in the emulsion, (ii) and gross weight (iii);
(b) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from those that step (a) describes in (iv);
Wherein the significant quantity at polymerizable surfactants described in the described mixture is in step (a) and at least 20 weight % of the polymerizable surfactants total amount that adds (b), to produce the pressure sensitive adhesive that average particulate size is less than or equal to 200nm;
(c) continuously pre--the emulsion of preparation in the step (a) is joined in the mixture of preparation in the step (b), with polymerization described pre--emulsion forms latex emulsion, wherein described pre--add additional polymerization starter between the polymerization period of emulsion; With
(d) with the pH of suitable alkali adjusting latex emulsion, making pH is 6.5 to 9.
2. the process of claim 1 wherein described pre--emulsion in the amount of monomer (i) be 70 to 90 weight %.
3. the method for claim 2, wherein described pre--emulsion in the amount of monomer (i) be 75 to 85 weight %.
4. the process of claim 1 wherein described pre--emulsion in monomer amount (ii) be 4 to 8 weight %.
5. the process of claim 1 wherein described pre--emulsion in monomer amount (iii) be 5 to 18 weight %.
6. the process of claim 1 wherein that described pressure sensitive adhesive has the average particulate size that is less than or equal to 100nm.
7. the process of claim 1 wherein that described monomer (i) is selected from Isooctyl acrylate monomer, vinylformic acid 4-methyl-2-pentyl ester, vinylformic acid 2-methyl butyl ester, vinylformic acid isopentyl ester, sec-butyl acrylate, n-butyl acrylate, 2-EHA, isodecyl methacrylate, vinylformic acid ester in the different ninth of the ten Heavenly Stems, isodecyl acrylate or its mixture.
8. the method for claim 7, wherein said monomer (i) is selected from n-butyl acrylate, 2-EHA or its mixture.
9. the process of claim 1 wherein that described monomer (ii) is selected from monoene monocarboxylic acid, monoene dicarboxylic acid or its mixture.
10. the method for claim 9, wherein said monomer (ii) is selected from vinylformic acid, methacrylic acid, fumaric acid, toxilic acid, methylene-succinic acid, Ba Dousuan or its mixture.
11. the method for claim 10, wherein said monomer (ii) are selected from vinylformic acid, methacrylic acid or its mixture.
12. the process of claim 1 wherein that described monomer (iii) is selected from methyl acrylate, methyl methacrylate, ethyl propenoate or its mixture.
13. the method for claim 12, wherein said monomer (iii) are selected from methyl acrylate, methyl methacrylate or its mixture.
14. the total amount water-soluble or the water dispersible polymerizable surfactants that the process of claim 1 wherein in step (a) and add (b) account for described pre--emulsion in monomer (i), (ii) and gross weight (iii) be 0.1 to 5 weight %.
15. the method for claim 14, wherein the total amount water-soluble or the water dispersible polymerizable surfactants that adds in step (a) and (b) account for described pre--emulsion in monomer (i), (ii) and gross weight (iii) be 0.5 to 2 weight %.
16. the method for claim 1, wherein said polymerizable surfactants possess hydrophilic property part and hydrophobic parts, described hydrophilic parts is selected from sulfonate allylamine part, vitriol allylamine part or phosphoric acid salt allylamine part and described hydrophobic parts is selected from-R or have general formula R O-(CH
2CH
2O)
n-group; Wherein R is the phenyl of alkyl group or alkyl-replacement, and wherein to have 1 to 20 carbon atom and n be 2 to 100 integer to this alkyl group.
17. the method for claim 16, wherein n is 2 to 15 integer.
18. the process of claim 1 wherein that described polymerizable surfactants is the allyl amine salt with alkyl benzene sulphonate (ABS) of following general formula:
Wherein, R
1Be alkyl group with 1 to 20 carbon atom, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
19. the method for claim 18, wherein said polymerizable surfactants are the allyl amine salt of Witco 1298 Soft Acid.
20. the process of claim 1 wherein that described polymerizable surfactants is the alkyl oxide vitriolic allyl amine salt with following general formula:
Wherein, R
2Be the alkyl group with 1 to 20 carbon atom, n is 2 to 100 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
21. the method for claim 20, wherein n is 2 to 15 integer.
22. the method for claim 21, wherein said polymerizable surfactants are lauryl ether vitriolic allyl amine salt.
23. the process of claim 1 wherein that described polymerizable surfactants is the allyl amine salt with phosphoric acid ester of following general formula:
Wherein, R
3Be the phenyl of alkyl or alkyl-replacement, wherein this alkyl group has 1 to 20 carbon atom, and n is 2 to 100 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
24. the method for claim 23, wherein n is 2 to 15 integer.
25. the method for claim 24, wherein said polymerizable surfactants are the allyl amine salt of nonyl phenol ethoxylate phosphoric acid ester.
26. the process of claim 1 wherein that described polymerizable surfactants is the vitriolic allyl amine salt with following general formula:
R
6-SO
3 - +X-CH
2-CH＝CH
2
Wherein, R
6Be alkyl group with 6 to 20 carbon atoms, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
27. the method for claim 26, wherein R
6It is alkyl group with 10 to 18 carbon atoms.
28. the process of claim 1 wherein that described polymerizable surfactants is the phenyl compound with replacement of following general formula:
Wherein, R
7Be alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
8Be hydrogen atom or alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
9Be hydrogen atom or propenyl group; A is the alkylidene group that comprises 2 to 4 carbon atoms unsubstituted or that replace; N is 1 to 200 integer; With M be basic metal, ammonium ion or alkanolamine residue.
29. the method for claim 28, wherein said polymerizable surfactants are the phenyl compounds with replacement of following general formula:
30. the method for claim 29, wherein R
7Be C
6-18Alkyl, A are that ethylidene and M are basic metal or ammonium.
31. the method for claim 30, wherein R
7Be nonyl, n be 10 to 30 and M be ammonium.
32. the process of claim 1 wherein that described polymerizable surfactants is poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether with following general formula:
Wherein, R
10It is the alkyl group that comprises 8 to 30 carbon atoms; R
11Be hydrogen or methyl; A is the alkylidene group with 2 to 4 carbon atoms unsubstituted or that replace; N is 0 or 1 to 200 integer; With M be basic metal, ammonium ion or alkanolamine residue.
33. the method for claim 32, wherein said polymerizable surfactants are poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ethers with following general formula:
Wherein, R
10It is the alkyl group that comprises 8 to 14 carbon atoms; With n be 1 to 200 integer.
34. the process of claim 1 wherein described adding polymerization starter total amount based on described pre--monomer (i) in the emulsion, (ii) and gross weight (iii) be 0.01 to 0.5 weight %.
35. the method for claim 1, its also be included in monomer (i), (ii) and transformation efficiency (iii) be higher than and in described latex emulsion, add C after 90%
2To C
12The vinyl ester of carboxylic acid.
36. the method for claim 35, wherein monomer (i), (ii) and transformation efficiency (iii) in described latex emulsion, add described vinyl ester after being higher than 95%.
37. the method for claim 1, it also is included in advance-and the adding of emulsion adds C after finishing in described latex emulsion
2To C
12The vinyl ester of carboxylic acid.
38. the contact adhesive composition with water-whitening resistance of raising, it comprises the aqueous emulsion polymkeric substance according to the method preparation of claim 1.
39. the contact adhesive composition with water-whitening resistance of raising, it comprises the aqueous emulsion polymkeric substance according to the method preparation of claim 35.
40. contact adhesive composition with water-whitening resistance of raising, it comprises the aqueous emulsion polymkeric substance, described polymkeric substance comprises the polyreaction product of polymerisable aqueous emulsion, and this polymerisable aqueous emulsion comprises: (i) (methyl) vinylformic acid C of at least a hydrophobic alcohol
4-14Alkyl ester, the (ii) at least a hydrophilic monomer of 2-10 weight %, (iii) (methyl) vinylformic acid C of the hydrophilic alcohol of at least a part of 5-20 weight %
1-2Alkyl ester, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer in the described emulsion (i), (ii) and gross weight (iii);
Wherein, after described polymerization, the pH of described polymkeric substance be adjusted to pH be 6.5 to 9 and the average particulate size of described polymkeric substance be less than or equal to 200nm.
41. the composition of claim 40, wherein the amount of monomer (i) is 70 to 90 weight % in described emulsion.
42. the composition of claim 41, wherein the amount of monomer (i) is 75 to 85 weight % in described emulsion.
43. the composition of claim 40, wherein monomer amount (ii) is 4 to 8 weight % in described emulsion.
44. the composition of claim 40, wherein monomer amount (iii) is 5 to 18 weight % in described emulsion.
45. the composition of claim 40, wherein said pressure sensitive adhesive has the average particulate size that is less than or equal to 100nm.
46. the composition of claim 40, wherein said monomer (i) are selected from Isooctyl acrylate monomer, vinylformic acid 4-methyl-2-pentyl ester, vinylformic acid 2-methyl butyl ester, vinylformic acid isopentyl ester, sec-butyl acrylate, n-butyl acrylate, 2-EHA, isodecyl methacrylate, vinylformic acid ester in the different ninth of the ten Heavenly Stems, isodecyl acrylate or its mixture.
47. the composition of claim 46, wherein said monomer (i) is selected from n-butyl acrylate, 2-ethylhexyl acrylate or its mixture.
48. the composition of claim 40, wherein said monomer (ii) are selected from monoene monocarboxylic acid, monoene dicarboxylic acid or its mixture.
49. the composition of claim 48, wherein said monomer (ii) are selected from vinylformic acid, methacrylic acid, fumaric acid, toxilic acid, methylene-succinic acid, Ba Dousuan or its mixture.
50. the composition of claim 49, wherein said monomer (ii) are selected from vinylformic acid, methacrylic acid or its mixture.
51. the composition of claim 40, wherein said monomer (iii) are selected from methyl acrylate, methyl methacrylate, ethyl propenoate or its mixture.
52. the composition of claim 51, wherein said monomer (iii) are selected from methyl acrylate, methyl methacrylate or its mixture.
53. the composition of claim 40, the total amount of the water-soluble or water dispersible polymerizable surfactants that wherein between polymerization period, exists based on the monomer in the described emulsion (i), (ii) and gross weight (iii) be 0.1 to 5 weight %.
54. the composition of claim 53, the total amount of the water-soluble or water dispersible polymerizable surfactants that wherein between polymerization period, exists based on the monomer in the described emulsion (i), (ii) and gross weight (iii) be 0.5 to 2 weight %.
55. the composition of claim 53, wherein the amount of the water-soluble or water dispersible polymerizable surfactants that with described monomer (i), (ii) and (iii) adds based on the total amount of the water-soluble or water dispersible polymerizable surfactants that between polymerization period, exists less than 80 weight %.
56. the composition of claim 40, wherein said polymerizable surfactants possess hydrophilic property part and hydrophobic parts, described hydrophilic parts is selected from sulfonate allylamine part, vitriol allylamine part or phosphoric acid salt allylamine part and described hydrophobic parts is selected from-R or have general formula R O-(CH
2CH
2O)
n-group; Wherein R is the phenyl of alkyl group or alkyl-replacement, and wherein to have 1 to 20 carbon atom and n be 2 to 100 integer to this alkyl group.
57. the composition of claim 56, wherein n is 2 to 15 integer.
58. the composition of claim 40, wherein said polymerizable surfactants are the allyl amine salt with alkyl benzene sulphonate (ABS) of following general formula:
Wherein, R
1Be alkyl group with 1 to 20 carbon atom, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
59. the composition of claim 58, wherein said polymerizable surfactants are the allyl amine salt of Witco 1298 Soft Acid.
60. the composition of claim 40, wherein said polymerizable surfactants are the alkyl oxide vitriolic allyl amine salt with following general formula:
Wherein, R
2Be the alkyl group with 1 to 20 carbon atom, n is 2 to 100 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
61. the composition of claim 60, wherein n is 2 to 15 integer.
62. the composition of claim 61, wherein said polymerizable surfactants are lauryl ether vitriolic allyl amine salt.
63. the composition of claim 40, wherein said polymerizable surfactants are the allyl amine salt with phosphoric acid ester of following general formula:
Wherein, R
3Be the phenyl of alkyl or alkyl-replacement, wherein this alkyl group has 1 to 20 carbon atom, and n is 2 to 100 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
64. the composition of claim 63, wherein n is 2 to 15 integer.
65. the composition of claim 64, wherein said polymerizable surfactants are the allyl amine salt of nonyl phenol ethoxylate phosphoric acid ester.
66. the composition of claim 40, wherein said polymerizable surfactants are the vitriolic allyl amine salt with following general formula:
R
6-SO
3 - +X-CH
2-CH＝CH
2
Wherein, R
6Be alkyl group with 6 to 20 carbon atoms, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
67. the composition of claim 66, wherein R
6It is alkyl group with 10 to 18 carbon atoms.
68. the composition of claim 40, wherein said polymerizable surfactants are the phenyl compounds with replacement of following general formula:
Wherein, R
7Be alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
8Be hydrogen atom or alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
9Be hydrogen atom or propenyl group; A is the alkylidene group that comprises 2 to 4 carbon atoms unsubstituted or that replace; N is 1 to 200 integer; With M be basic metal, ammonium ion or alkanolamine residue.
69. the composition of claim 68, wherein said polymerizable surfactants are the phenyl compounds with replacement of following general formula:
70. the method for claim 69, wherein R
7Be C
6-18Alkyl, A are that ethylidene and M are basic metal or ammonium.
71. the method for claim 70, wherein R
7Be nonyl, n be 10 to 30 and M be ammonium.
72. the composition of claim 40, wherein said polymerizable surfactants are poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ethers with following general formula:
Wherein, R
10It is the alkyl group that comprises 8 to 30 carbon atoms; R
11Be hydrogen or methyl; A is the alkylidene group with 2 to 4 carbon atoms unsubstituted or that replace; N is 0 or 1 to 200 integer; With M be basic metal, ammonium ion or alkanolamine residue.
73. the composition of claim 72, wherein said polymerizable surfactants are poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ethers with following general formula:
Wherein, R
10It is the alkyl group that comprises 8 to 14 carbon atoms; With n be 1 to 200 integer.
74. the composition of claim 40, the total amount of the polymerization starter of wherein said adding based on the monomer in the described emulsion (i), (ii) and gross weight (iii) be 0.01 to 0.5 weight %.
75. the composition of claim 40, wherein said polyreaction product also be included in monomer (i), (ii) and transformation efficiency (iii) be higher than the C that is added into after 90% in the described polyreaction product
2To C
12The vinyl ester of carboxylic acid.
76. the composition of claim 75, wherein said polyreaction product also be included in monomer (i), (ii) and transformation efficiency (iii) be higher than the C that is added into after 95% in the described polyreaction product
2To C
12The vinyl ester of carboxylic acid.
77. prepare the method for the pressure sensitive adhesive of the water-whitening resistance with raising, it comprises:
(a) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from compound, the phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether or its mixture with terminal allylamine part;
(b) in the mixture of step (a), add monomer and randomly additional water continuously, with the resulting emulsion of polymerization to form latex emulsion, wherein additional polymerization starter of adding and wherein said monomer comprise during described letex polymerization: (i) (methyl) vinylformic acid C of at least a hydrophobic alcohol
4-14Alkyl ester, the (ii) at least a hydrophilic monomer of 2-10 weight %, (iii) (methyl) vinylformic acid C of the hydrophilic alcohol of at least a part of 5-20 weight %
1-2Alkyl ester and (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from those that describe in the step (a), wherein monomer (i), (ii) and weight % (iii) be based on monomer (i), (ii) and gross weight (iii);
Wherein the significant quantity at polymerizable surfactants described in the mixture of step (a) is in step (a) and at least 20 weight % of the polymerizable surfactants total amount that adds (b), is less than or equal to the pressure sensitive adhesive of 200nm with the production median size; With
(c) with the pH of suitable alkali adjusting latex emulsion, making pH is 6.5 to 9.
78. the method for claim 77, wherein the amount of monomer (i) is 70 to 90 weight %.
79. the method for claim 78, wherein the amount of monomer (i) is 75 to 85 weight %.
80. the method for claim 77, wherein monomer amount (ii) is 4 to 8 weight %.
81. the method for claim 77, wherein monomer amount (iii) is 5 to 18 weight %.
82. the method for claim 77, wherein said pressure sensitive adhesive has the average particulate size that is less than or equal to 100nm.
83. the method for claim 77, wherein said monomer (i) are selected from Isooctyl acrylate monomer, vinylformic acid 4-methyl-2-pentyl ester, vinylformic acid 2-methyl butyl ester, vinylformic acid isopentyl ester, sec-butyl acrylate, n-butyl acrylate, 2-EHA, isodecyl methacrylate, vinylformic acid ester in the different ninth of the ten Heavenly Stems, isodecyl acrylate or its mixture.
84. the method for claim 83, wherein said monomer (i) is selected from n-butyl acrylate, 2-EHA or its mixture.
85. the method for claim 77, wherein said monomer (ii) are selected from monoene monocarboxylic acid, monoene dicarboxylic acid or its mixture.
86. the method for claim 85, wherein said monomer (ii) are selected from vinylformic acid, methacrylic acid, fumaric acid, toxilic acid, methylene-succinic acid, Ba Dousuan or its mixture.
87. the method for claim 86, wherein said monomer (ii) are selected from vinylformic acid, methacrylic acid or its mixture.
88. the method for claim 77, wherein said monomer (iii) are selected from methyl acrylate, methyl methacrylate, ethyl propenoate or its mixture.
89. the method for claim 88, wherein said monomer (iii) are selected from methyl acrylate, methyl methacrylate or its mixture.
90. the method for claim 77, wherein the total amount of the water-soluble or water dispersible polymerizable surfactants that adds in step (a) and (b) based on the monomer (i) that adds, (ii) and gross weight (iii) be 0.1 to 5%.
91. the method for claim 90, wherein the total amount of the water-soluble or water dispersible polymerizable surfactants that adds in step (a) and (b) based on the monomer (i) that adds, (ii) and gross weight (iii) be 0.5 to 2 weight %.
92. the method for claim 77, wherein said polymerizable surfactants possess hydrophilic property part and hydrophobic parts, described hydrophilic parts is selected from sulfonate allylamine part, vitriol allylamine part or phosphoric acid salt allylamine part and described hydrophobic parts is selected from-R or have general formula R O-(CH
2CH
2O)
n-group; Wherein R is the phenyl of alkyl group or alkyl-replacement, and wherein to have 1 to 20 carbon atom and n be 2 to 100 integer to this alkyl group.
93. the method for claim 92, wherein n is 2 to 15 integer.
94. the method for claim 77, wherein said polymerizable surfactants are the allyl amine salt with alkyl benzene sulphonate (ABS) of following general formula:
Wherein, R
1Be alkyl group with 1 to 20 carbon atom, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
95. the method for claim 94, wherein said polymerizable surfactants are the allyl amine salt of Witco 1298 Soft Acid.
96. the method for claim 77, wherein said polymerizable surfactants are the alkyl oxide vitriolic allyl amine salt with following general formula:
Wherein, R
2Be the alkyl group with 1 to 20 carbon atom, n is 2 to 100 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
97. the method for claim 96, wherein n is 2 to 15 integer.
98. the method for claim 97, wherein said polymerizable surfactants are lauryl ether vitriolic allyl amine salt.
99. the method for claim 77, wherein said polymerizable surfactants are the allyl amine salt with phosphoric acid ester of following general formula:
Wherein, R
3Be the phenyl of alkyl or alkyl-replacement, wherein this alkyl group has 1 to 20 carbon atom, and n is 2 to 100 integer, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
100. the method for claim 99, wherein n is 2 to 15 integer.
101. the method for claim 100, wherein said polymerizable surfactants are the allyl amine salt of nonyl phenol ethoxylate phosphoric acid ester.
102. the method for claim 77, wherein said polymerizable surfactants are the vitriolic allyl amine salt with following general formula:
R
6-SO
3 - +X-CH
2-CH＝CH
2
Wherein, R
6Be alkyl group with 6 to 20 carbon atoms, and X
+Be selected from
+NH
3,
+NH
2R
4Perhaps
+NHR
4R
5, R wherein
4And R
5Be independently selected from C
1-C
4Alkyl or hydroxyalkyl group.
103. the method for claim 102, wherein R
6It is alkyl group with 10 to 18 carbon atoms.
104. the method for claim 77, wherein said polymerizable surfactants are the phenyl compounds with replacement of following general formula:
Wherein, R
7Be alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
8Be hydrogen atom or alkyl, alkenyl or the aralkyl that comprises 6 to 18 carbon atoms; R
9Be hydrogen atom or propenyl group; A is the alkylidene group that comprises 2 to 4 carbon atoms unsubstituted or that replace; N is 1 to 200 integer; With M be basic metal, ammonium ion or alkanolamine residue.
105. the method for claim 104, wherein said polymerizable surfactants are the phenyl compounds with replacement of following general formula:
106. the method for claim 105, wherein R
7Be C
6-18Alkyl, A are that ethylidene and M are basic metal or ammonium.
107. the method for claim 106, wherein R
7Be nonyl, n be 10 to 30 and M be ammonium.
108. the method for claim 77, wherein said polymerizable surfactants are poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ethers with following general formula:
Wherein, R
10It is the alkyl group that comprises 8 to 30 carbon atoms; R
11Be hydrogen or methyl; A is the alkylidene group with 2 to 4 carbon atoms unsubstituted or that replace; N is 0 or 1 to 200 integer; With M be basic metal, ammonium ion or alkanolamine residue.
109. the method for claim 108, wherein said polymerizable surfactants are poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ethers with following general formula:
Wherein, R
10It is the alkyl group that comprises 8 to 14 carbon atoms; With n be 1 to 200 integer.
110. the method for claim 77, the total amount of the polymerization starter of wherein said adding based on the monomer (i) that adds, (ii) and gross weight (iii) be 0.01 to 0.5 weight %.
111. the method for claim 77, its also be included in monomer (i), (ii) and transformation efficiency (iii) be higher than and in described latex emulsion, add C after 90%
2To C
12The vinyl ester of carboxylic acid.
112. the method for claim 111, wherein monomer (i), (ii) and transformation efficiency (iii) in described latex emulsion, add described vinyl ester after being higher than 95%.
113. the method for claim 77, it also is included in monomeric adding and adds C after finishing in described latex emulsion
2To C
12The vinyl ester of carboxylic acid.
114. the contact adhesive composition with water-whitening resistance of raising, it comprises the aqueous emulsion polymkeric substance according to the method preparation of claim 77.
115. the contact adhesive composition with water-whitening resistance of raising, it comprises the aqueous emulsion polymkeric substance according to the method preparation of claim 111.
116. prepare the method for the pressure sensitive adhesive of the water-whitening resistance with raising, it comprises:
(a) form polymerisable moisture pre--emulsion, it comprises: (i) at least a hydrophobic alkyl acrylate of 70 to 90 weight %, it is selected from n-butyl acrylate, 2-ethylhexyl acrylate or its mixture, the (ii) at least a hydrophilic monomer of 2 to 10 weight %, it is selected from vinylformic acid, methacrylic acid or its mixture, the (iii) methyl acrylate of 5 to 20 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on described pre--monomer (i) in the emulsion, (ii) and gross weight (iii);
(b) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from those that step (a) describes in (iv);
Wherein the significant quantity at polymerizable surfactants described in the described mixture is in step (a) and at least 20 weight % of the polymerizable surfactants total amount that adds (b), is less than or equal to the pressure sensitive adhesive of 200nm with the production median size;
(c) continuously pre--the emulsion of preparation in the step (a) is joined in the mixture of preparation in the step (b), with polymerization described pre--emulsion forms latex emulsion, wherein described pre--add additional polymerization starter between the polymerization period of emulsion; With
(d) with the pH of suitable alkali adjusting latex emulsion, making pH is 6.5 to 9.
117. contact adhesive composition with water-whitening resistance of raising, it comprises the aqueous emulsion polymkeric substance, described polymkeric substance comprises the polyreaction product of polymerisable aqueous emulsion, this polymerisable aqueous emulsion comprises: (i) at least a hydrophobic acrylic acid's alkyl ester of 70 to 90 weight %, it is selected from n-butyl acrylate, 2-ethylhexyl acrylate or its mixture, the (ii) at least a hydrophilic monomer of 2 to 10 weight %, it is selected from vinylformic acid, methacrylic acid or its mixture, the (iii) methyl acrylate of 5 to 20 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from the compound with terminal allylamine part, phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether, perhaps its mixture, wherein monomer (i), (ii) and weight % (iii) be based on monomer in the described emulsion (i), (ii) and gross weight (iii);
Wherein, after described polymerization, the pH of described polymkeric substance be adjusted to pH be 6.5 to 9 and the average particulate size of described polymkeric substance be less than or equal to 200nm.
118. prepare the method for the pressure sensitive adhesive of the water-whitening resistance with raising, it comprises:
(a) polymerization starter of the water-soluble of water, significant quantity or water dispersible polymerizable surfactants and original bulk is contacted form mixture, wherein said water-soluble or water dispersible polymerizable surfactants is selected from compound, the phenyl compound with replacement of at least one alkenyl substitutents, poly suboxygen alkyl-1-(allyloxy methyl) sulfated alkyl ether or its mixture with terminal allylamine part;
(b) in the mixture of step (a), add monomer and randomly additional water continuously, with the resulting emulsion of polymerization to form latex emulsion, wherein between the polymerization period of described emulsion, add additional polymerization starter, comprise with wherein said monomer: (i) at least a hydrophobic acrylic acid's alkyl ester of 70 to 90 weight %, it is selected from n-butyl acrylate, 2-ethylhexyl acrylate or its mixture, the (ii) at least a hydrophilic monomer of 2 to 10 weight %, it is selected from vinylformic acid, methacrylic acid or its mixture, the (iii) methyl acrylate of 5 to 20 weight %, (iv) water-soluble or water dispersible polymerizable surfactants, it is selected from those that describe in the step (a), wherein monomer (i), (ii) and weight % (iii) be based on monomer (i), (ii) and gross weight (iii);
Wherein the significant quantity at polymerizable surfactants described in the mixture of step (a) is in step (a) and at least 20 weight % of the polymerizable surfactants total amount that adds (b), is less than or equal to the pressure sensitive adhesive of 200nm with the production median size; With
(c) with the pH of suitable alkali adjusting latex emulsion, making pH is 6.5 to 9.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30517401P | 2001-07-13 | 2001-07-13 | |
| US60/305,174 | 2001-07-13 | ||
| US32398401P | 2001-09-21 | 2001-09-21 | |
| US60/323,984 | 2001-09-21 | ||
| US10/142,455 | 2002-05-10 | ||
| US10/142,455 US7169846B2 (en) | 2001-07-13 | 2002-05-10 | Process for improving water-whitening resistance of pressure sensitive adhesives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1553924A CN1553924A (en) | 2004-12-08 |
| CN1294169C true CN1294169C (en) | 2007-01-10 |
Family
ID=27385807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028178394A Expired - Lifetime CN1294169C (en) | 2001-07-13 | 2002-07-11 | Process for improving water-whitening resistance of pressure sensitive adhesives |
Country Status (10)
| Country | Link |
|---|---|
| US (3) | US7169846B2 (en) |
| EP (1) | EP1409561B1 (en) |
| JP (1) | JP2004534894A (en) |
| KR (1) | KR20040054659A (en) |
| CN (1) | CN1294169C (en) |
| AT (1) | ATE337345T1 (en) |
| CA (1) | CA2452882A1 (en) |
| DE (1) | DE60214190T2 (en) |
| ES (1) | ES2266536T3 (en) |
| WO (1) | WO2003006518A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296398C (en) * | 2004-02-10 | 2007-01-24 | 上海明田纸塑有限公司 | Supertransparent self-adhesive latex product and its production method and use |
| US20060100357A1 (en) * | 2004-11-09 | 2006-05-11 | Bunn Andrew G | Water-based adhesives for difficult substrates and low temperatures |
| JP4358190B2 (en) * | 2005-03-16 | 2009-11-04 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
| BRPI0601352A (en) | 2005-04-25 | 2006-12-26 | Rohm & Haas | composition and method of preparing a composition |
| US7531595B2 (en) * | 2006-03-08 | 2009-05-12 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing silica nanoparticles |
| US7645827B2 (en) * | 2006-03-08 | 2010-01-12 | 3M Innovative Properties Company | High shear pressure-sensitive adhesive |
| WO2007138108A1 (en) * | 2006-06-01 | 2007-12-06 | Cytec Surface Specialties, S.A. | Pressure sensitive adhesives |
| WO2008064724A1 (en) * | 2006-12-01 | 2008-06-05 | Cytec Surface Specialties, S.A. | Pressure sensitive adhesives |
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| US9688780B2 (en) * | 2014-08-08 | 2017-06-27 | Rhodia Operations | Allyl ether sulfate polymerizable surfactants and methods for use |
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- 2002-07-11 AT AT02749946T patent/ATE337345T1/en not_active IP Right Cessation
- 2002-07-11 JP JP2003512286A patent/JP2004534894A/en active Pending
- 2002-07-11 CA CA002452882A patent/CA2452882A1/en not_active Abandoned
- 2002-07-11 DE DE60214190T patent/DE60214190T2/en not_active Expired - Lifetime
- 2002-07-11 ES ES02749946T patent/ES2266536T3/en not_active Expired - Lifetime
- 2002-07-11 KR KR10-2004-7000370A patent/KR20040054659A/en not_active Application Discontinuation
- 2002-07-11 CN CNB028178394A patent/CN1294169C/en not_active Expired - Lifetime
- 2002-07-11 WO PCT/US2002/021958 patent/WO2003006518A1/en active IP Right Grant
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2006
- 2006-12-19 US US11/641,488 patent/US20070100069A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| US20070100068A1 (en) | 2007-05-03 |
| DE60214190T2 (en) | 2006-12-28 |
| EP1409561B1 (en) | 2006-08-23 |
| US20030100670A1 (en) | 2003-05-29 |
| WO2003006518A1 (en) | 2003-01-23 |
| US7169846B2 (en) | 2007-01-30 |
| ES2266536T3 (en) | 2007-03-01 |
| DE60214190D1 (en) | 2006-10-05 |
| ATE337345T1 (en) | 2006-09-15 |
| US20070100069A1 (en) | 2007-05-03 |
| US20080249239A9 (en) | 2008-10-09 |
| CA2452882A1 (en) | 2003-01-23 |
| JP2004534894A (en) | 2004-11-18 |
| EP1409561A1 (en) | 2004-04-21 |
| KR20040054659A (en) | 2004-06-25 |
| CN1553924A (en) | 2004-12-08 |
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